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Freddy Tjosås 《Tetrahedron》2007,63(48):11893-11901
Alkylation of aromatic rings is a major challenge in organic syntheses since more complex carbon skeletons can be constructed. The alkylation of pyridine by nucleophilic aromatic substitution of the nitro group in methyl 3-nitro-4-pyridylcarboxylate (1) with malonic ester is reported. The versatility of the α-(3-pyridyl) malonic ester product (3) is demonstrated by the formation of a number of new 3-alkylated pyridines and new fused bis-heterocycles. cis 2-Halomethyl-4-(3-pyridyl)tetrahydrofuran products were selectively prepared. Exact 1H and 13C NMR assignments of practically all products were obtained by a series of NMR experiments.  相似文献   

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The synthesis and liquid crystalline properties of new series of 1,2,4‐ and 1,3,4‐oxadiazole derivatives (2a–f and 5a–f respectively) are reported. These compounds contain only one terminal flexible alkoxy chain, the other terminal substituent is a protecting benzyl group. All compounds of series 2 exhibit an enantiotropic nematic phase. The homologue with the longest chain (2f) displays an enantiotropic dimorphism smectic A– nematic. None of the compounds of series 5 shows mesomorphism and only crystal–isotropic transitions were observed. The liquid crystalline properties were investigated by differential scanning calorimetry, polarizing optical microscopy and X‐ray measurements. Luminescence properties, in chloroform solution, of 2f and the series 5 compounds were evaluated. Good photoluminescence quantum yields for compounds of series 5 were observed. Compound 2f, incorporating the 1,2,4‐oxadiazole ring shows a very strong reduction in emissive properties.  相似文献   

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Halide base perovskite LiCdX3 (X = F, Cl) is tested by CASTEP (Cambridge Serial Total Energy Package) based on density function theory (DFT). The presented discussion is to explore the structural, electronic, and optical properties of LiCdX3 (X = F, Cl). The calculated values of the lattice parameter are found to be 3.8 Å and 5.27 Å of LiCdF3 and LiCdCl3 respectively. The ideal structure of LiCdX3 (X = F, Cl) is cubic and dynamically stable. Electronic properties show that materials are semiconductors. The results from band structure are further evaluated by the total and partial density of states. The partial and total density of states confirms the degree of localization of electrons. In optical properties, the highest absorption coefficient is observed in LiCdCl3. The material is half metallic and has a narrow indirect band gap which may be used in photovoltaic applications.  相似文献   

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We describe a practical, multigram synthesis of (2Z,6Z,10Z,14Z,18E,22E)-3,7,11,15,19,23,27-heptamethyl-2,6,10,14,18,22,26-octacosaheptaen-1-ol [(Z(4),E(2),ω)-heptaprenol, 4] using the nerol-derived sulfone 8 as the key intermediate. Sulfone 8 is prepared by the literature route and is converted in five additional steps (18% yield from 8) to (Z(4),E(2),ω)-heptaprenol 4. The use of Eu(hfc)(3) as an NMR shift reagent not only enabled confirmation of the structure and stereochemistry of 4, but further enabled the structural assignment to a major side product from a failed synthetic connection. The availability by this synthesis of (Z(4),E(2),ω)-heptaprenol 4 in gram quantities will enable preparative access to key reagents for the study of the biosynthesis of the bacterial cell envelope.  相似文献   

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Organic/inorganic hybrid materials prepared by the sol–gel approach have rapidly become a fascinating new field of research in materials science. The explosion of activity in this area in the past decade has made tremendous progress in both the fundamental understanding of the sol–gel process and the development and applications of new organic/inorganic hybrid materials. Polymer-inorganic nanocomposite present an interesting approach to improve the separation properties of polymer material because they possess properties of both organic and inorganic such as good permeability, selectivity, mechanical strength, and thermal and chemical stability. Composite material derived by combining the sol–gel approach and organic polymers synthesis of hybrid material were the focus area of review It has also been demonstrated in this review that a more complete understanding of their structure–property behavior can be gained by employing many of the standard tools that are utilized for developing similar structure–property relationships of organic polymers. This review article is introductory in nature and gives introduction to composite materials/nanocomposite, their applications and the methods commonly employed for their synthesis and characterization. A brief literature survey on the polysaccharide templated and polysaccharide/protein dual templated synthesis of silica composite materials is also presented in this review article.  相似文献   

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Research on Chemical Intermediates - Innovative hybrid composites based on poly (4,4'-Diaminodiphenyl sulfone) (PDDS) and TiO2 nanoparticles have been synthesized. The samples have been...  相似文献   

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The present paper gives an overview of the properties and performance of membranes of a poly(ether ether ketone) derivative with a cardo group in the chain, known in the literature as PEEKWC or PEK-C. This is one of the typical examples of a new polymer, emerged in the last two decades, with the potential to be applied as a membrane material in a wide range of application fields. Due to the presence of the cardo group in the backbone, the polymer is soluble in several common organic solvents, in contrast to the traditional poly(ether ketone) (PEK) and poly(ether ether ketone) (PEEK). It is therefore more versatile and its solubility allows the use of nonsolvent-induced phase inversion techniques to prepare membranes with a wide range of different morphologies and transport characteristics. The present review will show the current state of the art and will testify that PEEKWC offers interesting perspectives in especially the fields of gas separation, biomedical applications and—in its sulfonated form-in fuel cells. Examples of successful application in microfiltration, ultrafiltration, nanofiltration, pervaporation, membrane contactors, catalytic membranes and some other applications, such as packaging and molecular imprinting will also be shown.  相似文献   

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Volatile dimethylgold(III) β-iminovinylthionates, (CH3)2Au(CH3CSCHC(NH)CH3) (I) and (CH3)2Au(CF3CSCHC(NH)CH3) (II), were studied. For complexes I and II, the synthesis is described and data from elemental analysis, IR and UV/Vis spectra, DTA, and X-ray diffraction are given. The structures of I and II are composed of monomeric complexes combined into polymeric stack-type associates. The distorted square environment of gold is formed by sulfur and nitrogen atoms of the chelating ligand and two carbon atoms of the methyl groups. For complex I, the average Au-S bond length is 2.260 Å, the Au-N bond length is 2.137 Å, and the chelate angle SAuN is 94.1°; for II, these values are 2.355 Å, 2.088 Å, and 93.7°, respectively.  相似文献   

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The effect of preparation methods on the formation of gold doped ceria–lanthana solid solution (Au-CLSS) nanoparticles (NPs) was studied. The nanoparticles were prepared by surfactant assisted precipitation methods viz., co-precipitation (CP) and deposition precipitation (DP) in the presence of cetyltrimethylammonium bromide (CTAB). The as prepared nanoparticles were characterized using BET, FESEM, EDS, Raman, TEM, XRD and UV–Vis. spectroscopic techniques to investigate the preferred method for the preparation of nanoparticles for catalytic applications. The cubic fluorite phase formation of nanoparticles was confirmed by XRD analysis and the average crystallite size was calculated to be around 7–10 nm. Surface area studies revealed that the NPs formed by CTAB assisted method have higher surface area. The morphology of NPs formed by both methods was flaky. Raman studies confirmed that the samples prepared by DP method generated increased oxygen vacancies than those prepared by CP method. In the present work, catalytic oxidation efficiency of the catalysts studied with toluene vapours showed maximum efficiency for Au-CLSS at low temperatures (450 K) as compared to undoped CLSS.  相似文献   

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Calcium titanium phosphate (CTP) was prepared by the sol–gel route in order to prepare suitable coatings. This work addresses the question of how to prepare stable CTP sols. Their rheological properties as a function of process parameters like solid loading and water content are investigated. It was found that an increased solid loading as well as an increased water content lead to an increased initial viscosity as well as a more pronounced ageing induced viscosity rise. In addition, the thermal behavior of the resulting xerogels was analyzed. Furthermore, we studied the ion release behavior of the xerogels when brought in contact with water. Results suggest that calcium titanium phosphate shows a diffusion controlled ion release mode with a preferential release of Ca.  相似文献   

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